CN1279520A - Lithium secondary battery - Google Patents
Lithium secondary battery Download PDFInfo
- Publication number
- CN1279520A CN1279520A CN00109178A CN00109178A CN1279520A CN 1279520 A CN1279520 A CN 1279520A CN 00109178 A CN00109178 A CN 00109178A CN 00109178 A CN00109178 A CN 00109178A CN 1279520 A CN1279520 A CN 1279520A
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- China
- Prior art keywords
- battery
- electrolyte
- benzene
- methyl
- propyl
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 95
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 238000003475 lamination Methods 0.000 claims abstract 2
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 30
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 claims description 27
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 20
- -1 cycloalkyl benzene derivative Chemical class 0.000 claims description 13
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 claims description 10
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 10
- SPPWGCYEYAMHDT-UHFFFAOYSA-N 1,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)C)C=C1 SPPWGCYEYAMHDT-UHFFFAOYSA-N 0.000 claims description 8
- 150000001721 carbon Chemical group 0.000 claims description 7
- 150000001555 benzenes Chemical class 0.000 claims description 5
- 238000005192 partition Methods 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 101000648997 Homo sapiens Tripartite motif-containing protein 44 Proteins 0.000 claims 2
- 102100028017 Tripartite motif-containing protein 44 Human genes 0.000 claims 2
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 39
- 230000000996 additive effect Effects 0.000 abstract description 33
- 150000004997 alkyl benzene derivatives Chemical class 0.000 abstract description 2
- 230000002411 adverse Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000008151 electrolyte solution Substances 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 40
- 229910013870 LiPF 6 Inorganic materials 0.000 description 37
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 36
- 230000008859 change Effects 0.000 description 22
- 239000000203 mixture Substances 0.000 description 21
- 239000012046 mixed solvent Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000002002 slurry Substances 0.000 description 8
- 230000006399 behavior Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 150000001491 aromatic compounds Chemical class 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- YRGAYAGBVIXNAQ-UHFFFAOYSA-N 1-chloro-4-methoxybenzene Chemical compound COC1=CC=C(Cl)C=C1 YRGAYAGBVIXNAQ-UHFFFAOYSA-N 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000009931 harmful effect Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- QUBJDMPBDURTJT-UHFFFAOYSA-N 3-chlorothiophene Chemical compound ClC=1C=CSC=1 QUBJDMPBDURTJT-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910013733 LiCo Inorganic materials 0.000 description 2
- 229910010586 LiFeO 2 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910012672 LiTiO Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000009783 overcharge test Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/574—Devices or arrangements for the interruption of current
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/574—Devices or arrangements for the interruption of current
- H01M50/578—Devices or arrangements for the interruption of current in response to pressure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/574—Devices or arrangements for the interruption of current
- H01M50/581—Devices or arrangements for the interruption of current in response to temperature
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2200/00—Safety devices for primary or secondary batteries
- H01M2200/10—Temperature sensitive devices
- H01M2200/106—PTC
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
Abstract
A lithium secondary battery including an electrode assembly composed of positive and negative electrode plates, and a clapboard lamination therebetween in the cell casing, and the lithium secondary battery is disposed in a cell casing filled with electrolyte containing lithium salt dissolved in organic solvent, wherein the cell casing is provided with a current interrupt device for cutting off a charge current of the battery when an internal gas pressure of the battery exceeds a predetermined value, and wherein the organic solvent contains alkylbenzene derivative or cycloalkylbenzene derivative having tertiary carbon adjacent a phenyl group. To secure the safety of a battery by using an additive agent that, when added to an electrolytic solution, effectively acts on an overcharge without adversely affecting battery characteristics such as low-temperature characteristics and preservation characteristics.
Description
The present invention relates to a kind of employing and dissolved lithium storage battery as the electrolyte of the lithium salts of solute in organic solvent, adopting overcharges also can guarantee the lithium storage battery of safe electrolyte even particularly relate to.
In recent years, along with the miniaturization and the lightweight of electronic instrument, also require to want miniaturization and as the battery of power supply.For this reason, as discharging and recharging possible battery, small-sized light weight and high power capacity be that the lithium storage battery of representative begins practicability with the lithium ion battery, in portable electronic, communication instruments such as small-sized gamma camera, cell-phone, notebook computer, use.
This kind lithium storage battery adopts the carbon-based material that can absorb, break away from lithium ion as negative electrode active material, as positive active material, adopts LiCoO
2, LiNiO
2, LiMn
2O
4, LiFeO
2Deng containing the lithium reducing metal oxide, adopted at organic solvent dissolution electrolyte as the lithium salts of solute, after the battery assembling, the lithium ion of emitting from positive active material by primary charging enters into and becomes the possible battery of charging in the carbon particle.
In such lithium storage battery, after overcharging, follow to enter overcharge condition, extract superfluous lithium out from positive pole, the surplus that produces lithium at negative pole is inserted, and makes positive and negative the two poles of the earth produce the instability of heat.When positive and negative the two poles of the earth produce hot instability, will make the organic solvent of electrolyte decompose soon, produce rapid exothermic reaction, produce the state of the unusual heat release of battery, damage the fail safe of battery.This situation is along with the energy density of lithium storage battery increases and more become important problem.
In order to solve such problem, by in electrolyte, add a spot of aromatic compound as additive, can guarantee the fail safe of overcharging, for example open the content that proposes relevant this respect in flat 7-No. 302614 communiques the spy.Open in the report that flat 7-No. 302614 communiques are proposed the spy, negative pole adopts carbon materials, additive as electrolyte, use molecular weight below 500, had aromatic compounds such as the methyl phenyl ethers anisole derivative invertibity oxidation-reduction potential, that have the pi-electron track on the high current potential of the anodal current potential when completely charging.Such aromatic compound is protected battery by preventing to overcharge.
Guarantee the motion of the fail safe of overcharging by in electrolyte, adding additive, for example open in flat 9-No. 106835 communiques and also proposed the spy.Open in the report that flat 9-No. 106835 communiques are proposed the spy; negative pole adopts carbon materials; additive as electrolyte; biphenyl, 3-R-thiophene, 3-chlorothiophene, furans etc. have been used on a small quantity; by the cell voltage copolymerization more than the maximum actuation voltage of battery; improve the builtin voltage of battery, can when overcharging, protect battery.
But, open in the motion of flat 7-No. 302614 communiques the spy, though the methyl phenyl ethers anisole derivative has effective function to overcharging, producing has dysgenic problem to battery behaviors such as cyclophysis and storage characteristics.Again, aromatic compound is oxidation Decomposition under the voltage about 4.5V, will produce gas; form copolymerization simultaneously; preventing the additives for overcharge protection battery on the other hand like this,, might produce the dissolving of its copolymer and can not prevent the situation of overcharging according to the composition of electrolyte.As a result, we can say that the aromatic compounds such as methyl phenyl ethers anisole derivative with pi-electron track might not suppress to overcharge.
On the other hand, open in the motion of flat 9-No. 106835 communiques the spy, as the biphenyl of additive use, because polarity is low, and low to the dissolubility of electrolyte, during the low temperature action, an additive part is separated out the problem that causes that battery behavior reduces.Again, 3-chlorothiophene has excitant, and strong stench is arranged, and further also there is the problem of easy oxidation Decomposition in difficulty during processing, and furans is oxidation Decomposition easily also, and that a kind of compound all exists has dysgenic problem to battery behavior.
For this reason, the present invention is just at the invention of the problems referred to above, can harmful effect not arranged even its purpose is to adopt to add yet in electrolyte, and the additive of useful effect is arranged overcharging, guarantee the fail safe of battery battery behaviors such as low-temperature characteristics and storage characteristics.
In order to achieve the above object, lithium storage battery of the present invention reaches the electric current partition seal body that setting pressure cuts off charging when above for comprise air pressure when inside battery in battery case, comprises benzene derivative or cycloalkyl benzene derivative with the tertiary carbon atom that abuts against phenyl in organic solvent.At this, abut against the benzene derivative or the cycloalkyl benzene derivative of the tertiary carbon atom of phenyl, be active owing to abut against the tertiary carbon atom of phenyl, reactive high, so under the state that the hydrogen atom on the tertiary carbon atom is overcharging, deviate from easily.For this reason, decompose the generation that is swift in response when reaching overcharge condition, produce hydrogen, copolyreaction simultaneously preferentially generates copolymer.
Then, because when having produced hydrogen, the air pressure of inside battery reaches each level pressure power when above, and electric current cuts off the seal body action and cuts off and charge, so can prevent to overcharge.
In view of the above,, can the decomposition of electrolyte be prevented trouble before it happens, guarantee safe state by in organic solvent, adding these additives.And the copolymer that is generated under overcharge condition is as the resistive element effect, and this copolymer is to be difficult to dissolved substances again in electrolyte simultaneously, and useful effect can be arranged overcharging.
Again, these additives that add in organic solvent are liquid at normal temperatures, the polarity height, and to the dissolubility height of electrolyte, additive can not separated out in electrolyte when battery moved at low temperature.For this reason, even in electrolyte, add such additive, can not reduce battery behavior yet.As a result,, can harmful effect not arranged to battery behaviors such as low-temperature characteristics and storage characteristics if adopt in organic solvent and lithium salts adds the electrolyte of such additive simultaneously, promptly can deterioration, just can guarantee the fail safe of battery.
And as the abovementioned alkyl benzene derivative, it is desirable selecting use from isopropylbenzene, 1,3-diisopropylbenzene (DIPB), 1,4-diisopropylbenzene (DIPB), 1-methyl propyl benzene, 1,3-two (1-methyl-propyl) benzene, 1,4-two (1-methyl-propyl) benzene.As above-mentioned cycloalkyl benzene derivative, preferably from cyclohexyl benzene, cyclopenta benzene, select use.
It below is brief description of drawings
Fig. 1 is for representing to have got involved the dividing plate of the embodiment with electrolyte of the present invention, reel positive and negative pole plate that overlaps and the cutaway view that is encased in the state in the outer tinning.
Fig. 2 is contained in the partial sectional view of battery partition seal body of the peristome of outer tinning for expression.
Among the figure, 10-negative plate, 10a-negative pole current collection joint, 20-positive plate, 20a-anodal current collection joint, 30-dividing plate, 40-outer tinning, 41-pad, 42-outer tinning cut off seal body with insulation spacer, 50-electric current.
Embodiments of the invention below are described.
The following embodiment that lithium storage battery of the present invention is described according to Fig. 1 and Fig. 2.At this, Fig. 1 has got involved the dividing plate of the embodiment with electrolyte of the present invention for expression, the positive and negative pole plate that reel to overlap also is encased in the cutaway view of the state in the outer tinning, and Fig. 2 is contained in the partial sectional view of battery partition seal body of the peristome of outer tinning for expression.1. the making of negative plate
After negative electrode active material that will be made of native graphite (d=3.36 ) and the bonding agent that is made of Kynoar (PVDF) etc. are dissolved in the organic solvent that is made of N-methyl-2-pyrrolidones (NMP) etc., mix, be modulated into slurries or paste.Adopt two coaters when becoming slurries, scrape lodicule, adopt rolling method when becoming paste, slurries or paste evenly are coated on whole of two sides of metallic core (for example thickness is the Copper Foil of 20 μ m), form the negative plate that has applied active material.
Then, allow the negative plate that has applied active material by in the drying machine, necessary organic solvent is removed by drying in the time of will making slurries or paste.Then, roll dry negative plate 10 with roll squeezer, making thickness is the negative plate 10 of 0.14mm.2. the making of positive plate
On the other hand, will be by LiCoO
2The bonding agent that carbon elements such as the positive active material that constitutes, acetylene carbon black, graphite are conductive agent, be made of Kynoar (PVDF) is dissolved in by after in the organic solvent of N-methyl-2-constitute than pyrrolidone (NMP) etc., mix, be modulated into slurries or paste.
Adopt two coaters when becoming slurries, scrape lodicule, adopt rolling method when becoming paste, slurries or paste evenly are coated on whole of two sides of metallic core (for example thickness is the Copper Foil of 20 μ m), form the positive plate that has applied active material.Then, allow the positive plate that has applied active material by in the drying machine, necessary organic solvent is removed by drying in the time of will making slurries or paste.After the drying, roll dry positive plate 20 with roll squeezer, making thickness is the positive plate 20 of 0.17mm.3. the making of electrode body
Between the negative plate 10 and positive plate 20 of above-mentioned making, put into the low and cheap polyolefin-based resins of the reaction of organic solvent and constitute micro-porous film, preferably polyethylene microporous film (for example thickness is 0.025mm) 30, and consistent coincidence of center line of Width that allows each pole plate 10,20.Afterwards, reel, fix with adhesive tape, be made into scroll electricity body at most peripheral with unillustrated up-coiler among the figure.4. the adjustment of electrolyte (1) embodiment 1
In the mixed solvent that ethylene carbonate (EC) 40 weight portions and diethyl carbonate (DEC) 60 weight portions are constituted, add LiPF as derivative salt
61mol/ rises and mixes, and further adds the isopropylbenzene 2 weight % that represent with the structural formula of following change 1 and carries out hybrid modulation electrolyte, is made into the electrolyte a of embodiment 1.
[changing 1]
(2) embodiment 2
Equally, in the mixed solvent that EC 40 weight portions and DEC 60 weight portions are constituted, add 1mol/ and rise LiPF
6Mix, further add 1,3-diisopropyl benzene, the 2 weight % that represent with the structural formula of following change 2 and carry out hybrid modulation electrolyte, be made into the electrolyte b of embodiment 2.
[changing 2]
(3) embodiment 3
Equally, in the mixed solvent that EC 40 weight portions and DEC 60 weight portions are constituted, add 1mol/ and rise LiPF
6Mix, further add 1,4-diisopropylbenzene (DIPB), the 2 weight % that represent with the structural formula of following change 3 and carry out hybrid modulation electrolyte, be made into the electrolyte c of embodiment 3.
[changing 3]
(4) embodiment 4
Equally, in the mixed solvent that EC 40 weight portions and DEC 60 weight portions are constituted, add 1mol/ and rise LiPF
6Mix, further add 1-methyl propyl benzene, the 2 weight % that represent with the structural formula of following change 4 and carry out hybrid modulation electrolyte, be made into the electrolyte d of embodiment 4.
[changing 4]
(5) embodiment 5
Equally, in the mixed solvent that EC 40 weight portions and DEC 60 weight portions are constituted, add 1mol/ and rise LiPF
6Mix, further add 1,3-two (1-methyl-propyl) the benzene 2 weight % that represent with the structural formula of following change 5 and carry out hybrid modulation electrolyte, be made into the electrolyte e of embodiment 5.
[changing 5]
(6) embodiment 6
Equally, in the mixed solvent that EC 40 weight portions and DEC 60 weight portions are constituted, add 1mol/ and rise LiPF
6Mix, further add 1,4-two (1-methyl-propyl) the benzene 2 weight % that represent with the structural formula of following change 6 and carry out hybrid modulation electrolyte, be made into the electrolyte f of embodiment 6.
[changing 6]
(7) embodiment 7
Equally, in the mixed solvent that EC 40 weight portions and DEC 60 weight portions are constituted, add 1mol/ and rise LiPF
6Mix, further add the cyclohexylbenzene 2 weight % that represent with the structural formula of following change 7 and carry out hybrid modulation electrolyte, be made into the electrolyte g of embodiment 7.
[changing 7]
(8) embodiment 8
Equally, in the mixed solvent that EC 40 weight portions and DEC 60 weight portions are constituted, add 1mol/ and rise LiPF
6Mix, further add the cyclopenta benzene 2 weight % that represent with the structural formula of following change 8 and carry out hybrid modulation electrolyte, be made into the electrolyte h of embodiment 8.
[changing 8]
(9) comparative example 1
In the mixed solvent that EC 40 weight portions and DEC 60 weight portions are constituted, add 1mol/ and rise LiPF
6Mix, be modulated into non-additive electrolyte, be made into the electrolyte x of comparative example 1.(10) comparative example 2
In the mixed solvent that EC 40 weight portions and DEC 60 weight portions are constituted, add 1mol/ and rise LiPF
6Mix, further add biphenyl (C
12H
10) 2 weight % carry out hybrid modulation electrolyte, are made into the electrolyte y of comparative example 2.(11) comparative example 3
In the mixed solvent that EC 40 weight portions and DEC 60 weight portions are constituted, add 1mol/ and rise LiPF
6Mix, further add 4-chloroanisole, 2 weight % and carry out hybrid modulation electrolyte, be made into the electrolyte z of comparative example 3.5. the making of lithium storage battery
Then, as shown in Figure 1, the electrode body of above-mentioned making dispose insulation board 41 respectively up and down after, the peristome of tinning 40 outside the steel that is configured as double as negative terminal cylindraceous with a plate punch process inserts this electrode body.Then, the inner bottom part of tinning 40 outside the negative pole current collection joint 10a that will extend out from the negative plate 10 of electrode body is welded to, the anodal current collection joint 20a that will extend out from the positive plate 20 of electrode body is welded to the bottom that electric current cuts off the base plate 54 of seal body 50 simultaneously.
In addition, as shown in Figure 2, electric current cuts off seal body 50 by the positive cover 51 of the stainless steel that is configured as teabowl with a cover shape (cap-like) and base plate 54 formations that are configured as bowl-shape stainless steel.Positive cover 51 is made of protuberance 52 that protrudes to outside batteries and the flat flange portion 53 that constitutes the edge part of this protuberance 52, is provided with a plurality of venthole 52a in the bight of protuberance 52.On the other hand, base plate 54 is made of with the flat flange portion 56 that constitutes the bottom side portion of this recess 55 recess 55 to the inside battery expansion.Be provided with venthole 55a in the bight of recess 55.
In the inside of these positive cover 51 and base plate 54, take in pressure rises when inside battery and the electric power of distortion is derived plate 57 when above to setting pressure.This electric power is derived plate 57 and is made of recess 57a and flange portion 57b, is that the concavo-convex of 0.2mm surface constitutes for the aluminium foil of 0.005mm by thickness for example.The lowest part of recess 57a is adapted to the upper surface of the recess 55 of base plate 54 and contacts, and flange portion 57b is clamped between the flange portion 56 of the flange portion 53 of positive cover 51 and base plate 54.In addition, positive cover 51 and base plate 54 do not allow liquid spill by the seal body of polypropylene (PP) system with insulation spacer 59 sealings.
Be equipped with PTC (positive temperature coefficient) temperature-sensitive element 58 on the part on the top of flange portion 57b, when having overcurrent to flow through in the battery abnormal heating phenomenon takes place, the resistance value of this PTC temperature-sensitive element 58 increases and reduces overcurrent.Then since when the pressure rises of inside battery is above to setting pressure electric power derive the recess 57a distortion of plate 57, cut off the contact between the recess 55 of electric power derivation plate 57 and base plate 54, thus partition overcurrent or short circuit current.
Then, after injecting above-mentioned electrolyte a～h and x, y, z respectively from the peristome of outer tinning 40, the outer tinning that gets involved polypropylene (PP) system on the peristome of tinning outside 40 cuts off seal body 50 with insulation spacer 42 mounting electric currents, the upper end of the peristome of outer tinning 40 is cut off the riveted joint of seal body 50 1 sides at electric current seal and do not allow liquid spill, be made into 11 kinds of cylindrical shape lithium storage batteries respectively.The nominal capacity of each lithium storage battery A～H of Zhi Zuoing and X, Y, Z is 1350mAh like this.
At this, battery A has represented to inject the battery of the electrolyte a of embodiment 1, battery B has represented to inject the battery of the electrolyte b of embodiment 2, battery C has represented to inject the battery of the electrolyte c of embodiment 3, battery D has represented to inject the battery of the electrolyte d of embodiment 4, battery E has represented to inject the battery of the electrolyte e of embodiment 5, battery F has represented to inject the battery of the electrolyte f of embodiment 6, battery G has represented to inject the battery of the electrolyte g of embodiment 7, battery H has represented to inject the battery of the electrolyte h of embodiment 8, battery X has represented to inject the battery of the electrolyte x of comparative example 1, battery Y has represented to inject the battery of the electrolyte y of comparative example 2, and battery Z has represented to inject the battery of the electrolyte z of comparative example 3.6. test (1) overcharge test
With 11 kinds of lithium storage battery A～H of above-mentioned making and X, Y, Z with the charging current for charging of 1350mA (1C) till allow cell voltage be 4.1V, the constant-potential charge with 4.1V became fully charged state in 3 hours then.The charging current that flows into 2700mA (2C) between each positive and negative electrode terminal of 11 kinds of each lithium storage batteries after the so full charging is overcharged, and measures to begin from overcharging to cut off the time and the maximum temperature of each battery at this moment till seal body 50 actions to electric current.Its result is as shown in table 1.(2) low-temperature characteristics
With 11 kinds of lithium storage battery A～H of above-mentioned making and X, Y, Z at room temperature (25C) with the charging current for charging of 1350mA (1C) till allow cell voltage be 4.1V, the constant-potential charge with 4.1V became fully charged state in 3 hours then.Then, after at room temperature stopping 3 hours, at room temperature with the discharging current of 1350mA (1C) discharge into allow final voltage be 2.75V till, according to the discharge capacity of calculating discharge time under the room temperature.
On the other hand, with 11 kinds of lithium storage battery A～H of above-mentioned making and X, Y, Z at room temperature (25 ℃) with the charging current for charging of 1350mA (1C) till allow cell voltage be 4.1V, the constant-potential charge with 4.1V became fully charged state in 3 hours then.Then, after under 0 ℃, stopping 3 hours, discharge into the discharging current of 1350mA (1C) under 0 ℃ allow final voltage be 2.75V till, according to the discharge capacity of calculating discharge time under the low temperature (mAh).
Then, each discharge capacity that goes out according to aforementioned calculation, with respect to the shared ratio of the discharge capacity (mAh) under the discharge capacity under the room temperature (mAh) low temperature as low-temperature characteristics, and calculate according to following formula (formula 1), its result is as shown in table 1.
Low-temperature characteristics=(discharge capacity under the discharge capacity/room temperature under the low temperature) * 100% ... (1) (3) storage characteristic
With 11 kinds of lithium storage battery A～H of above-mentioned making and X, Y, Z at room temperature (25 ℃) with the charging current for charging of 1350mA (1C) till allow cell voltage be 4.1V, the constant-potential charge with 4.1V became fully charged state in 3 hours then.Then, after under 60 ℃ environment, storing 20 days, with the discharging current of 1350mA (1C) discharge into allow cell voltage be 2.75V till, according to the discharge capacity of calculating discharge time behind the high temperature storage.Then, with respect to the shared ratio of the discharge capacity behind the discharge capacity high temperature storage under the room temperature as storage characteristic, and calculate according to following formula (formula 2), its result is as shown in table 1.
Storage characteristic=(discharge capacity under the discharge capacity/room temperature behind the high temperature storage) * 100% ... (2)
Table 1
| Battery variety | Electrolyte (kind of solute amount of solvent (weight %) additive) | Electric current cuts off the time (branch) | Maximum temperature (℃) | Low-temperature characteristics (%) | Storage characteristic (%) |
| ?A | ?1M?LiPF 6(EC: DEC=4: 6) 2% isopropylbenzene | 15 | ?74 | ?83 | ?91 |
| ?B | ?1M?LiPF 6(EC: DEC=4: 6) 2% 1,3-diisopropylbenzene (DIPB) | 17 | ?81 | ?83 | ?92 |
| ?C | ?1M?LiPF 6(EC: DEC=4: 6) 2% 1,4-diisopropylbenzene (DIPB) | 17 | ?83 | ?84 | ?89 |
| ?D | ?1M?LiPF 6(EC: DEC=4: 6) 2% 1-methyl propyl benzene | 17 | ?78 | ?83 | ?90 |
| ?E | ?1M?LiPF 6(EC: DEC=4: 6) 2% 1,3-two (1-methyl-propyl) benzene | 18 | ?80 | ?81 | ?89 |
| ?F | ?1M?LiPF 6(EC: DEC=4: 6) 2% 1,4-two (1-methyl-propyl) benzene | 19 | ?82 | ?83 | ?91 |
| ?G | ?1M?LiPF 6(EC: DEC=4: 6) 2% cyclohexylbenzene | 15 | ?72 | ?85 | ?92 |
| ?H | ?1M?LiPF 6(EC: DEC=4: 6) 2% cyclopenta benzene | 17 | ?79 | ?84 | ?90 |
| ?X | ?1M?LiPF 6(EC: DEC=4: 6) do not have interpolation | 32 | Break | 85 | ?93 |
| ?Y | ?1M?LiPF
6(EC: DEC=4: 6) 2% | 20 | ?88 | ?60 | ?85 |
| ?Z | ?1M?LiPF 6(EC: DEC=4: 6) 2% 4-chloroanisole | 21 | ?90 | ?77 | ?65 |
Table 1 shows, break though adopt the battery X of the electrolyte x of the comparative example 1 that does not add additive to produce after back 32 minutes in the beginning of overcharging, when low-temperature characteristics and storage characteristic all good.Adopt the battery Y of electrolyte y of comparative example 2 of the biphenyl of existing additive to cut off charging current in the beginning of overcharging after 20 minutes, maximum temperature at this moment is 88 ℃, and low-temperature characteristics and storage characteristic all are in lower value.Further, adopt the battery Z of electrolyte z of comparative example 3 of 4-chloroanisole of existing additive to cut off charging current in the beginning of overcharging after 21 minutes, maximum temperature at this moment is 90 ℃, and low-temperature characteristics and storage characteristic all are in lower value.
On the other hand, the isopropylbenzene that has adopted the structural formula of above-mentioned [change 1] of additive of the present invention to represent, the structural formula of above-mentioned [change 2] represent 1,3-diisopropylbenzene (DIPB), the structural formula of above-mentioned [change 3] represent 1,4-diisopropylbenzene (DIPB), 1-methyl propyl benzene that the structural formula of above-mentioned [changing 4] is represented, the structural formula of above-mentioned [change 5] represent 1,3-two (1-methyl-propyl) benzene, 1,4-two (1-methyl-propyl) benzene that the structural formula of above-mentioned [changing 6] is represented, the cyclohexyl benzene that the structural formula of above-mentioned [changing 7] is represented, battery A～H of electrolyte a～h of the embodiment 1～embodiment 8 of the cyclopenta benzene that the structural formula of above-mentioned [changing 8] is represented, cut off charging current in the beginning of overcharging after 15～19 minutes, maximum temperature at this moment is 72～83 ℃ a low value, and low-temperature characteristics and storage characteristic are all good.
When reaching 4.1V, cell voltage overcharges when being in overcharge condition, isopropylbenzene, 1,3-diisopropylbenzene (DIPB), 1,4-diisopropylbenzene (DIPB), 1-methyl propyl benzene, 1,3-two (1-methyl-propyl) benzene, 1, additives such as 4-two (1-methyl-propyl) benzene, cyclohexyl benzene, cyclopenta benzene begin decomposition reaction, produce gas.Meanwhile, the beginning polymerization reaction produces heat of polymerization.Continue in this state to overcharge, will increase the generation of gas, cut off seal body 50 actions, cut off charging current from 15～19 minutes after-currents of beginning that overcharge.So also slowly reduce battery temperature.
Again, show, change additive and also do not find special difference by comparing battery A～battery H.Therefore, can preferably adopt the isopropylbenzene of representing from the structural formula of above-mentioned [changing 1], the structural formula of above-mentioned [change 2] represent 1,3-diisopropylbenzene (DIPB), the structural formula of above-mentioned [change 3] represent 1,4-diisopropylbenzene (DIPB), 1-methyl propyl benzene that the structural formula of above-mentioned [changing 4] is represented, the structural formula of above-mentioned [change 5] represent 1,3-two (1-methyl-propyl) benzene, 1,4-two (1-methyl-propyl) benzene that the structural formula of above-mentioned [changing 6] is represented, the cyclohexyl benzene that the structural formula of above-mentioned [changing 7] is represented is selected at least a kind of additive in the cyclopenta benzene that the structural formula of above-mentioned [changing 8] is represented.
Cyclohexyl benzene particularly, the maximum temperature when the beginning electric current that overcharges cuts off seal body 50 actions is low, the low-temperature characteristics excellence, and storage characteristic is good, and can be preferred.7. the discussion of electrolyte kind
Then, inquire into the influence that kind produced of used electrolyte.(1) embodiment 9
In the mixed solvent that EC 40 weight portions and dimethyl carbonate (DMC) 60 weight portions are constituted, add 1mol/ and rise LiPF
6Mix, further add the cyclohexyl benzene 2 weight % that represent with above-mentioned [changing 7] structural formula and carry out hybrid modulation electrolyte, be made into the electrolyte i of embodiment 9.(2) embodiment 10
In the mixed solvent that EC 40 weight portions and methyl ethyl carbonate (MEC) 60 weight portions are constituted, add 1mol/ and rise LiPF
6Mix, further add the cyclohexyl benzene 2 weight % that represent with above-mentioned [changing 7] structural formula and carry out hybrid modulation electrolyte, be made into the electrolyte j of embodiment 10.(3) embodiment 11
In the mixed solvent that EC 40 weight portions, DEC 30 weight portions and DMC 30 weight portions are constituted, add 1mol/ and rise LiPF
6Mix, further add the cyclohexyl benzene 2 weight % that represent with above-mentioned [changing 7] structural formula and carry out hybrid modulation electrolyte, be made into the electrolyte k of embodiment 11.(4) embodiment 12
The 0.5mol/ that adds as electrolytic salt in the mixed solvent that EC 40 weight portions and DEC 60 weight portions are constituted rises LiPF
6Rise LiBF with 0.5mol/
4Mix, further add the cyclohexyl benzene 2 weight % that represent with above-mentioned [changing 7] structural formula and carry out hybrid modulation electrolyte, be made into the electrolyte 1 of embodiment 12.
Then and above-mentioned same, inject above-mentioned electrolyte i～l in the tinning outside 40, the upper end of the peristome of outer tinning 40 is cut off the riveted joint of seal body 50 1 sides at electric current seal and do not allow liquid spill, be made into lithium storage battery I～L of embodiment 9～12.In addition, battery I has represented to inject the battery of the electrolyte i of embodiment 9, battery J has represented to inject the battery of the electrolyte j of embodiment 10, and battery K has represented to inject the battery of the electrolyte k of embodiment 11, and battery L has represented to inject the battery of the electrolyte 1 of embodiment 12.
Then and above-mentioned same, adopt these batteries I～L, implement and above-mentioned same overcharging, measure and begin from overcharging to cut off time and the maximum temperature of each battery I～L at this moment till seal body 50 moves to electric current, its result is as shown in table 2.Again and above-mentioned same, measure low-temperature characteristics and storage characteristic, its result is as shown in table 2.
Table 2
| Battery variety | Electrolyte (kind of solute amount of solvent (weight %) additive) | Electric current cuts off the time (branch) | Maximum temperature (℃) | Low-temperature characteristics (%) | Storage characteristic (%) |
| I | ?1M?LiPF 6(EC: DMC=4: 6) 2% cyclohexyl benzene | 15 | ?73 | ?84 | ?92 |
| J | ?1M?LiPF 6(EC: MEC=4: 6) 2% cyclohexyl benzene | 16 | ?74 | ?85 | ?91 |
| K | ?1M?LiPF 6(EC: DEC: DMC=4: 3: 3) 2% cyclohexyl benzene | 16 | ?76 | ?84 | ?91 |
| L | ?0．5MLiPF 6+0．5MLiBF 4(EC: DEC=4: 6) 2% cyclohexyl benzene | 16 | ?75 | ?82 | ?87 |
Above-mentioned table 2 shows, even the kind of the organic solvent of change electrolyte or the kind of solute, electric current cuts off time, maximum temperature, low-temperature characteristics and storage characteristic and does not also show special difference, and the kind that shows additive that cyclohexyl benzene constitutes and electrolyte has nothing to do and can bring into play same effect.In addition, though not expression in table 2, adopt cyclohexylbenzene additive in addition, promptly adopt isopropylbenzene, 1,3-diisopropylbenzene (DIPB), 1, additives such as 4-diisopropylbenzene (DIPB), 1-methyl propyl benzene, 1,3-two (1-methyl-propyl) benzene, 1,4-two (1-methyl-propyl) benzene, cyclopenta benzene have also obtained same effect.8. the discussion of the addition of additive
Inquire into the influence of the addition of additive below.(1) embodiment 13
In the mixed solvent that EC 40 weight portions and DEC 60 weight portions are constituted, add 1mol/ and rise LiPF
6Mix, further the cyclohexylbenzene 1 weight % that adds as additive carries out hybrid modulation electrolyte, is made into the electrolyte m of embodiment 13.(2) embodiment 14
In the mixed solvent that EC 40 weight portions and DEC 60 weight portions are constituted, add 1mol/ and rise LiPF
6Mix, further the cyclohexylbenzene 3 weight % that add as additive carry out hybrid modulation electrolyte, are made into the electrolyte n of embodiment 14.(3) embodiment 15
In the mixed solvent that EC 40 weight portions and DEC 60 weight portions are constituted, add 1mol/ and rise LiPF
6Mix, further the cyclohexyl benzene 5 weight % that add as additive carry out hybrid modulation electrolyte, are made into the electrolyte o of embodiment 15.(4) embodiment 16
In the mixed solvent that EC 40 weight portions and DEC 60 weight portions are constituted, add 1mol/ and rise LiPF
6Mix, further the cyclohexyl benzene 10 weight % that add as additive carry out hybrid modulation electrolyte, are made into the electrolyte p of embodiment 16.
Then and above-mentioned same, inject above-mentioned electrolyte m～p in the tinning outside 40, the upper end of the peristome of outer tinning 40 is cut off the riveted joint of seal body 50 1 sides at electric current seal and do not allow liquid spill, be made into lithium storage battery I～L of embodiment 13～16.In addition, battery M has represented to inject the battery of the electrolyte m of embodiment 13, battery N has represented to inject the battery of the electrolyte n of embodiment 14, and battery O has represented to inject the battery of the electrolyte o of embodiment 15, and battery P has represented to inject the battery of the electrolyte p of embodiment 16.
Then and above-mentioned same, adopt these batteries M～P, implement and above-mentioned same overcharging, measure and begin from overcharging to cut off time and the maximum temperature of each battery M～P at this moment till seal body 50 moves to electric current, its result is as shown in table 3.Again and above-mentioned same, measure low-temperature characteristics and storage characteristic, its result is as shown in table 3.This appearance 3 has also been listed the battery G that adds cyclohexyl benzene 2 weight %.
Table 3
| Battery variety | Electrolyte (kind of solute amount of solvent (weight %) additive) | Electric current cuts off the time (branch) | Maximum temperature (℃) | Low-temperature characteristics (%) | Storage characteristic (%) |
| M | 1M?LiPF 6(EC: DEC=4: 6) 1% cyclohexyl benzene | 16 | ?75 | ?85 | ?92 |
| G | ?1M?LiPF 6(EC: DEC=4: 6) 2% cyclohexyl benzene | 15 | ?72 | ?85 | ?92 |
| N | ?1M?LiPF 6(EC: DEC=4: 6) 3% cyclohexyl benzene | 15 | ?72 | ?85 | ?92 |
| ?1M?LiPF 6(EC: DEC=4: 6) 5% cyclohexyl benzene | 15 | ?72 | ?84 | ?91 | |
| P | ?1M?LiPF 6(EC: DEC=4: 6) 10% cyclohexyl benzene | 15 | ?71 | ?80 | ?88 |
Above-mentioned table 3 shows, if the addition of additive is in the scope of 1～10 weight %, electric current cuts off time, maximum temperature, low-temperature characteristics and storage characteristic and does not also show special difference, for this reason, the addition of wishing additive is in the scope of 1～10 weight %, preferably in the scope of 1～5 weight %.In addition, though not expression in table 3, adopt cyclohexylbenzene additive in addition, promptly adopt isopropylbenzene, 1,3-diisopropylbenzene (DIPB), 1, additives such as 4-diisopropylbenzene (DIPB), 1-methyl propyl benzene, 1,3-two (1-methyl-propyl) benzene, 1,4-two (1-methyl-propyl) benzene, cyclopenta benzene have also obtained same effect.
As mentioned above, if in electrolyte, add the cumene that structural formula with above-mentioned [changing 1] is represented, the structural formula of above-mentioned [change 2] represent 1,3-diisopropyl benzene, the structural formula of above-mentioned [change 3] represent 1,4-diisopropylbenzene (DIPB), 1-methyl propyl benzene that the structural formula of above-mentioned [changing 4] is represented, the structural formula of above-mentioned [change 5] represent 1,3-two (1-methyl-propyl) benzene, the structural formula of above-mentioned [change 6] represent 1, the benzene derivative of the tertiary carbon atom that phenyl such as 4-two (1-methyl-propyl) benzene are adjacent, perhaps has the cyclohexylbenzene that the structural formula of above-mentioned [change 7] is represented, the additive that the cycloalkyl benzene derivative of the tertiary carbon atom that the phenyl of the cyclopenta benzene that the structural formula of above-mentioned [changing 8] is represented etc. is adjoining is constituted, can harmful effect not arranged to cyclophysis and storage characteristic, and effective function is arranged overcharging, can not allow the fail safe that can guarantee battery under the situation of degradation of cell performance.
Again, in the above-described embodiments, though be to adopt native graphite (d=3.36 as negative electrode active material
) for example is illustrated, except that native graphite, also can use the carbon-based material that can absorb, break away from lithium ion, for example, carbon black, coke, vitreous carbon, carbon fiber or these sintered body.
Again, in the above-described embodiments, though be to adopt LiCoO as positive active material
2For example is illustrated, but remove LiCoO
2In addition, also can adopt the lithium-containing transition metal compound of accepting lithium ion as object, for example LiNiO
2, LiCo
xNi
(1-x)O
2, LiCrO
2, LiVO
2, LiMnO
2, α LiFeO
2, LiTiO
2, LiScO
2, LiYO
2, LiMn
2O
4Deng, particularly preferred LiNiO
2, LiCo
xNi
(1-x)O
2Use separately or these two or more mixing uses.
Further, as electrolyte, so long as in organic solvent, dissolved ion-conducting material as the lithium salts of solute, the ionic conductance height, for positive and negative each electrode chemically, stable on the electrochemistry, use possible temperature range wide and safe, low-cost, just can use.For example except that above-mentioned organic solvent, also can use propene carbonate (PC), sulfolane (SL), oxolane (THF), γ fourth lactones (GBL) etc. or these mixed solvent.Again, use the strong lithium salts of electron attractivity, remove above-mentioned LiPF as solute
6Perhaps LiBF
4In addition, also can use for example LiClO
4, LiAsF
6, LiCF
3SO
3, Li (CF
3SO
2)
2N, Li (C
2F
5SO
2)
2N, LiC
4F
9SO
3Deng.
Claims (4)
1. lithium storage battery, be in battery case, to comprise between positive pole and the negative pole getting involved the lithium storage battery that has dissolved in electrode body that the dividing plate lamination constitutes and the organic solvent as the electrolyte of the lithium salts of solute, it is characterized in that in described battery case, comprising that air pressure when inside battery reaches the electric current that setting pressure cuts off charging when above and cuts off seal body, in described organic solvent, comprise benzene derivative or cycloalkyl benzene derivative with the uncle's level carbon atom that abuts against phenyl.
2. lithium storage battery according to claim 1, it is characterized in that described benzene derivative is from isopropylbenzene, 1,3-diisopropylbenzene (DIPB), 1,4-diisopropylbenzene (DIPB), 1-methyl propyl benzene, 1,3-two (1-methyl-propyl) benzene, 1, select anyly in 4-two (1-methyl-propyl) benzene, described cycloalkyl benzene derivative is to select from cyclohexylbenzene, cyclopenta benzene.
3. according to claim 1 and 2 described lithium storage batteries, it is characterized in that being included in to contain lithium metal oxide as the anodal of positive active material with the negative pole of material with carbon element as negative electrode active material.
4. according to each described lithium storage battery in the claim 1～3, it is characterized in that described electric current cuts off seal body and comprises owing to overcurrent flows through the PTC element that increases resistance value and produce the electric power guide plate of distortion partition to described PTC energising after the inside battery pressure rises reaches more than the setting pressure.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP185554/1999 | 1999-06-30 | ||
| JP11185554A JP3113652B1 (en) | 1999-06-30 | 1999-06-30 | Lithium secondary battery |
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| Publication Number | Publication Date |
|---|---|
| CN1279520A true CN1279520A (en) | 2001-01-10 |
| CN1180505C CN1180505C (en) | 2004-12-15 |
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ID=16172848
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001091786A Expired - Lifetime CN1180505C (en) | 1999-06-30 | 2000-06-14 | Lithium secondary battery |
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| Country | Link |
|---|---|
| US (1) | US6632572B1 (en) |
| EP (1) | EP1065744B1 (en) |
| JP (1) | JP3113652B1 (en) |
| KR (1) | KR100637744B1 (en) |
| CN (1) | CN1180505C (en) |
| CA (1) | CA2313297C (en) |
| DE (1) | DE60018852T2 (en) |
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- 2000-06-29 EP EP00113811A patent/EP1065744B1/en not_active Expired - Lifetime
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- 2000-06-29 KR KR1020000036304A patent/KR100637744B1/en active IP Right Grant
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- 2000-06-30 HU HU0002546A patent/HUP0002546A3/en unknown
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| US10236537B2 (en) | 2014-04-21 | 2019-03-19 | Toyota Jidosha Kabushiki Kaisha | Non-aqueous electrolyte secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1065744A2 (en) | 2001-01-03 |
| CA2313297C (en) | 2009-02-24 |
| DE60018852D1 (en) | 2005-04-28 |
| JP3113652B1 (en) | 2000-12-04 |
| EP1065744B1 (en) | 2005-03-23 |
| KR20010007570A (en) | 2001-01-26 |
| HUP0002546A2 (en) | 2001-02-28 |
| DE60018852T2 (en) | 2006-03-30 |
| JP2001015155A (en) | 2001-01-19 |
| HUP0002546A3 (en) | 2002-11-28 |
| CA2313297A1 (en) | 2000-12-30 |
| EP1065744A3 (en) | 2002-03-13 |
| TW461129B (en) | 2001-10-21 |
| CN1180505C (en) | 2004-12-15 |
| US6632572B1 (en) | 2003-10-14 |
| HU0002546D0 (en) | 2000-08-28 |
| KR100637744B1 (en) | 2006-10-24 |
| HK1032147A1 (en) | 2001-07-06 |
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